CN110402273A

CN110402273A - Effect pigment

Info

Publication number: CN110402273A
Application number: CN201880017446.1A
Authority: CN
Inventors: N·内里斯谢尔; L·哈姆
Original assignee: Merck Patent GmbH
Current assignee: Merck Patent GmbH
Priority date: 2017-03-17
Filing date: 2018-03-16
Publication date: 2019-11-01
Also published as: DE102017002554A1; JP2020514511A; TW201902847A; WO2018167268A1; EP3596170A1

Abstract

The present invention relates to glaze and enamel stabilization effect pigment with sb oxide coating or sb oxide mixture, in glaze, enamel or ceramics or glass-like materials have improveds stability, especially be higher than 1000 DEG C at a temperature of.

Description

Effect pigment

The present invention relates to glaze stabilizations and enamel stabilizing effect pigment with sb oxide coating, in glaze, enamel In thinkling sound, ceramics or glass-like materials have improved stability, especially 1000 DEG C or more at a temperature of be stable.

In general, the mixture of effect pigment (such as pearlescent pigment) and ceramic frit is used for the dress in ceramic glaze Decorations application.Especially when being used for ceramic glaze at a high temperature of 1000 DEG C or more and especially so-called once sintered In use, effect pigment is appeared in without unbearable oxidizing fusion (sintering feed ingredient) and high temperature during destruction sintering process in method The aggressive conditions problem of composition.Therefore, past attempts are attempted to stablize the effect for such application by covering insulating protective layer Answer pigment.Stabilized second starting point is the appropriately combined of sintering feed and pearlescent pigment.

It must lead to tinting strength, tinting power in the ceramic glaze known in the art for being used to use in the case where 1000 DEG C of > by pearlescent pigment With the significant loss of pearl effect.In order to prevent in this way, these pigment must be encapsulated in additional protective layer, or by pearl Use of the delustering pigment in high temperature application is limited to the iron oxide-coated pearly-lustre in the engobe or fluxing agent being specifically modified Pigment.

For example, 220 509 A1 of EP is described and is passed through SnO₂And/or CeO₂Layer stablizes pearlescent pigment.

307 771 A1 of EP discloses the SnO adulterated using Au₂Layer is encapsulated pearlescent pigment for stable and novel dress Adorn effect.In order to realize required stabilisation, a large amount of oxide/oxide group must be all applied in the case of two kinds It closes.It has proven to advantageously apply the protective coating based on entire pigment about 5-30wt% amount.

39 32 424 C1 of DE discloses the pearlescent pigment/sintering feed contained and without additional absorbability pigment.However, The use scope of the pigment glass sintering material is only 700-900 DEG C of highest.

2 096 592 A of GB is described uses pearlescent pigment in the ceramic fluxing agent comprising sintering feed.But target is sintered Temperature and 1000 DEG C of > at a temperature of all do not discussed in the text using the particular problem of pearlescent pigment.

US patent 5,783,506, which describes, to use TiO in the ceramic fluxing agent of " leafing (leafing) "₂Or Fe₂O₃Coated mica pigment, i.e. preparation are made of sintering feed, dispersing agent, adhesive, mica and pearlescent pigment based on mica, With required viscosity.Invention in this US patent is that pearlescent pigment is moved to the table of glaze due to the addition of mica Face (leafing).

US 4,353,991 is disclosed in " sintered glass enamel " using the pearlescent pigment with 1-200 μm of granularity, base In sintering feed/pigment mixture weight, concentration 0.5-25.0wt%.However, these mixtures only can be in highest 538-760 It is used at a temperature of DEG C.

0 419 843 A1 of EP, which is described, uses pearlescent pigment in glass sintering material with the concentration of 5-20wt%.This makes It is 800-900 DEG C with temperature and is used for standard sintered for Fast Sintering or 700-800 DEG C.

CN 101462895A discloses the golden pearly-lustre face for using 10-60wt% at 1000-1200 DEG C in glaze Material.Sintering feed used herein constitutes as follows:

Disadvantageously the purposes is only limitted to the specific golden pearlescent pigment based on mica herein, and the gold pearlescent pigment Layer structure is not disclosed.Therefore, the type of available color and selection have received and greatly limit in CN101462895A.

198 59 420 A1 of DE discloses the modification engobe with pearl effect.Pottery is coated usually using engobe Device product and ceramic are to improve (main) surface by fineness or color.Modified engobe realizes better engobe to burning The adhesion strength of knot or un-sintered ceramic tile, pottery product and ceramic.The engobe includes the burning of 600-1200 DEG C of sintering range Ramming material and one or more pearlescent pigments.

DE-A 1 952 538 and 0 130 272 A1 of EP are described using Sb₂O₃It is pigment coated as absorbability, such as The coating of chrome yellow or plumbous chromate is to increase light and heat stability.Temperature highest is mentioned in text is respectively 175 DEG C and 325 DEG C.

The prior art is unknown to be had for pearlescent pigment in pearlescent pigment, such as glaze, enamel, ceramics or glass-like materials Effect and general protective layer, wherein using temperature >=1000 DEG C, and compared to unprotected when application (such as frit compositions) Pigment realizes stabilisation in the case where no technology changes.

Therefore, it is an object of the invention to stabilizing effect pigment, thus its >=1000 DEG C at a temperature of stablize and therefore It can be used for decoration glaze, enamel etc. without problems, and the optical property of effect pigment not to be damaged or only micro- because of stabilisation simultaneously It is damaged smallly.It is intended herein to pass through in the case where not being modified the sintering feed of workpiece or not changing work piece production process Protective layer stabilizes to realize.

Surprisingly it has been discovered that effect pigment, such as pearlescent pigment include at least one layer based on laminar substrate TiO₂And/or titanium oxynitride and/or other skilled in the art are known containing titanium mixed oxide and other optional layers, If stabilized if surface has sb oxide coating.The coating makes effect pigment stable at >=1000 DEG C and makes It obtains it and is used for enamel, glaze, pottery or ceramic etc. without problems, and have no adverse effect on optical properties.

Therefore, the present invention relates to the effect pigments based on laminar substrate, which is characterized in that in order to realize in glaze, pottery The heat and temperature stability improved in porcelain, enamel etc. is coated with it mixed comprising one or more sb oxides or sb oxide Close the coating of object.

The present invention also relates particularly to preparation, coating, ceramic tile, enamel, glaze, pottery, glassware and ceramic, packet Containing stabilized effect pigment of the present invention.

Effect pigment, which is coated one or more sb oxides, causes in ceramic applications the pigment compared to unstable face Expect the stability significantly improved.It is such to stabilize especially in 600-1200 DEG C of temperature, but particularly preferably at 1000-1200 DEG C It is apparent under temperature sintering.

Sb oxide coating can be made of sb oxide variant not of the same race.The coating is preferably by Sb_xO_yIt forms, wherein x =2 and y=3,4,5, especially Sb₂O₃、Sb₂O₄Or Sb₂O₅Or the mixture of the sb oxide.Preferred mixture is by Sb₂O₃ And Sb₂O₄、Sb₂O₄And Sb₂O₅Or Sb₂O₃、Sb₂O₄And Sb₂O₅Composition.Sb oxide layer is special preferably by a kind of only sb oxide It is not Sb₂O₃Or Sb₂O₄Or Sb₂O₅Composition.

Particularly preferably Sb₂O₄Coating.In Sb₂O₄Variant in, particularly preferred α-cervantite (α-Sb₂O₄), because It provides the best protection of confrontation >=1000 DEG C for effect pigment, and examines simultaneously in addition to static stabilization from toxicological point Worry is recognized as compared to such as Sb₂O₃It is slighter.

For stabilizing, depending on the type and/or corresponding granularity level of effect pigment to be stabilized, effect face Preferably on its surface, coating is based on effect pigment 5-50wt%, especially 5-30wt% and very particularly preferably 10-15wt% to material Sb oxide or sb oxide mixture.It is particularly preferred that the Sb with 10-15wt%₂O₄, especially α-Sb₂O₄Painting Layer.

Depending on granularity, the coating of effect pigment usually has the thickness of 1-100nm, especially 2-70nm and very special Not preferred 5-50nm.

Coating means that the surface of effect pigment coats completely in present patent application.

It is simple and easily operated that coating is applied to effect pigment.It is mixed for stabilized sb oxide or sb oxide Object is closed preferably to be selected from one or more soluble antimonic salts, be applied to effect pigment by wet-chemical precipitation reaction.Then in 400- The coated effect pigment of 1000 DEG C of temperature lower calcination, so that forming a variety of variants such as Sb of sb oxide₂O₃、Sb₂O₄Or Sb₂O₅(depending on calcination temperature).Each variant can be easily determined by XRD.

When wet coating is covered, effect pigment is suspended in water, and one kind or more is added at the pH for being suitable for hydrolysis The hydrolyzable antimonic salt of kind, preferably antimony (III) salt, such as SbCl₃.Selection makes sb oxide or sb oxide hydrate, so that its Direct precipitation is on effect pigment without secondary precipitation.By metered alkali and/or acid simultaneously, pH is made to generally remain perseverance It is fixed.Then effect pigment is separated, wash and is dried and optional calcination.In general, calcination temperature is 250-1000 DEG C, preferably 350- 900℃.If desired, finally pigment can also be sieved to set suitable granularity.

In principle, preparation can also carry out in one kettle way certainly, wherein coating sb oxide according to the present invention in effect It carries out in the preparation process of pigment itself, is calcined in advance without pairing effect pigment.

It is carried out in a fluidized bed reactor in addition, coating can also be coated by gas phase, for example, EP 0 can be used correspondingly The pearlescent pigment preparation method proposed in 045 851 and EP 0 106 235.

For example, using H₂The following precursor containing Sb of O steam hydrolysis can be used for this purpose: SbCl₃、SbF₃, n-butanol antimony (III), Ethyl alcohol antimony (III) or three (dimethylamino) antimony.

The invention further relates to the methods for preparing stabilized effect pigment according to the present invention.

It is preferably pearlescent pigment to stable effect pigment, coated interference pigment, there is transparent, translucent and/or opaque layer Multi-layer pigments or holographic pigment.Special stabilization is realized in the case where interference or silvery white effect effect pigment, it is described Pigment is by being coated with TiO₂And/or titanium oxynitride and/or other containing titanium mixed oxide and other layers optional of laminar substrate Composition.

In this application, titanium oxynitride refers to formula TiO_xN_yCompound, wherein x=0-2 and y=0-1 and in all cases 1≤x+y≤2。

Particularly preferably there is TiO_xN_yThe effect pigment of layer, wherein x>1.5 and y<0.5.Oxynitriding titanium layer can also for two kinds or More kinds of titanium oxynitride compounds or other mixtures containing titanium mixed oxide.In this case, titanium oxynitride compound It can mix in any proportion.

Suitable effect pigment especially pearlescent pigment, coated interference pigment or with transparent, translucent and/or opaque layer Multi-layer pigments (are based particularly on carrier), and the latter one are preferably flake.Such as flake TiO₂, synthetic mica (such as fluorine Phlogopite) or natural mica, doped or undoped glass flake, flake SiO₂, flake Al₂O₃Or platelet shaped iron oxide is Suitably.Glass flake can be made of all types of glass well known by persons skilled in the art, such as A glass, E glass, C glass Glass, ECR glass, used glass, glass pane, borosilicate glass,Glass, experimental glass or optical glass. The refractive index of glass flake is preferably 1.45-1.80, especially 1.50-1.70.Glass baseplate is particularly preferably by C glass, ECR glass Glass or borosilicate glass composition.

High temperature resistant thin slice, such as Al₂O₃、SiC、B₄C, BN, graphite, TiO₂And Fe₂O₃Thin slice is specially suitable.

Suitable substrate sheet for pearlescent pigment can be doped or undoped.If doping, dopant are preferred For or mixtures thereof Al, N, B, Ti, Zr, Si, In, Sn or Zn.In addition, from transition metal (V, Cr, Mn, Fe, Co, Ni, Cu, Y, Nb, Mo, Hf, Ta, W) other ions and ion from lanthanide series can be used as dopant.

In Al₂O₃In the case where, substrate is preferably undoped or doped with TiO₂、ZrO₂Or ZnO.Al₂O₃Thin slice is preferred For corundum.Suitable Al₂O₃Thin slice is preferably doped or undoped α-Al₂O₃Thin slice, especially TiO₂α-the Al of doping₂O₃It is thin Piece.If adulterating substrate, the ratio adulterated is preferably based on the 0.01-5 weight % of substrate, especially 0.10-3 weight %.

Size of carrier substrate itself is not important, and can match with specific application.In general, the thickness of laminar substrate Degree is 0.1-5 μm, especially 0.2-4.5 μm.Size on two other directions is usually between 1 and 1000 μm, preferably in 2 Hes Between 200 μm, and especially between 5 and 60 μm.

Each layer metal oxide, metal oxide hydrate, metal suboxides, metal, metal on carrier substrate The thickness of or mixtures thereof fluoride, metal nitride, metal oxynitrides is preferably 3-300nm, especially 20-200nm.

In preferred embodiments, it is transparent, translucent and/or not can be coated with one or more layers for the carrier of effect pigment Transparent layer, including metal oxide, metal oxide hydrate, metal suboxides, metal, metal fluoride, metal nitrogen Compound, metal oxynitrides or a mixture of these materials.Metal oxide, metal oxide hydrate, metal suboxides, Or mixtures thereof metal, metal fluoride, metal nitride or metal oxynitride layers can have low-refraction (refractive index < Or high refractive index (refractive index >=1.8) 1.8).Suitable metal oxide and metal oxide hydrate are those skilled in the art Metal oxide or metal oxide hydrate known to member, such as aluminium oxide, hydrated alumina, silica, silica water Close object, iron oxide, tin oxide, cerium oxide, zinc oxide, zirconium oxide, chromium oxide, titanium oxide, particularly titanium dioxide, titanium oxide water Close object and its mixture, such as ilmenite or false pseudobrookite.The metal suboxides that can be used are such as titanium suboxide.It closes Suitable metal fluoride is such as magnesium fluoride.The metal nitride or metal oxynitrides that can be used are such as Titanium, zirconium And/or the nitride or oxynitride of tantalum.Metal oxide, metal, metal fluoride and/or metal oxide hydrate layer and Metal oxide and/or metal oxide hydrate layer very particularly preferably is preferably applied on carrier.Further, it is also possible to deposit In the multilayer comprising high refractive index and low-refraction metal oxide, metal oxide hydrate, metal or metal fluoride layer Structure, wherein high refractive index layer and low-index layer preferably replace.It particularly preferably include high refractive index layer and low-index layer Layer heap is folded, and wherein these layer heaps are one or more of folded to be applied on carrier.Here high refractive index layer and low-refraction Layer sequence can with Carrier-matching, so that carrier is integrated in multilayered structure.In another embodiment, metal aoxidizes Object, metal silicate, metal oxide hydrate, metal suboxides, metal, metal fluoride, metal nitride or metal Oxynitride layer can be mixed or be adulterated with colorant.

Suitable colorant or other elements are such as inorganic colored pigments, such as nonferrous metal oxides, such as magnet Mine, chromium oxide (III) or colored pigment, for example, Thenard's Blue (Co/Al spinelle) or element such as yttrium or antimony, And the pigment usually from perovskite, pyrochlore, rutile and spinel structure.Pearlescent pigment comprising these layers is in its master Very big color change is shown in terms of body colour tune, and may be showed in many cases due to interference angle dependency Color change (changeable colors along with angle).

In preferred embodiments, the outer layer on carrier is high refractive index metal oxide.The outer layer can be in addition upper It is stacked on to state layer heap, or in the case where high refractive index supporter, can be the folded a part of layer heap, and for example by TiO₂、 Titanium suboxide, Fe₂O₃、SnO₂、ZnO、ZrO₂、Ce₂O₃、CoO、Co₃O₄、V₂O₅、Cr₂O₃And/or its mixture, such as ilmenite or False pseudobrookite composition.Particularly preferred TiO₂, there are also Fe₂O₃.If carrier sheet is coated with TiO₂, then TiO₂Preferably rutile-type Furthermore variant is anatase modifications.The method for preparing rutile be described in such as prior art U.S.5,433,779, In 0 271 767 B1 of U.S.4,038,099, U.S.6,626,989, DE 25 22 572 C2 and EP.In order to by TiO₂Conversion Thin stannic oxide layer (< 10nm) for rutile as additive is preferably in TiO₂It is applied in substrate sheet before precipitating.

Effect pigment is known and is in most cases commercially available and can pass through this field The preparation of standard method known to technical staff.Effect pigment is preferably prepared by wet chemical method, wherein can be used as preparation Pearlescent pigment and the known wet-chemical paint-on technique developed, such as it is described in DE 14 67 468, DE 19 59 998, DE 20 09 566,DE21 06 613,DE 22 14 545,DE 22 15 191,DE 22 44 298,DE 2313 331,DE 24 29 762,DE 25 22 572,DE 31 37 808,DE 31 37809,DE 31 51 343,DE 31 51 354,DE 31 In 51 355, DE 32 11 602, DE 32 35 017, EP 0 608 388, WO 98/53011.

Particularly preferred effect pigment has a structure that

Substrate sheet+TiO₂

Substrate sheet+titanium oxynitride

Substrate sheet+SiO₂+TiO₂

Substrate sheet+SnO₂+TiO₂

Substrate sheet+Cr₂O₃+TiO₂

Substrate sheet+Ce₂O₃+TiO₂

Substrate sheet+ZrO₂+TiO₂

Substrate sheet+TiO₂+Cr₂O₃

Substrate sheet+TiO₂+SiO₂+TiO₂

Substrate sheet+TiO₂+SiO₂

Substrate sheet+TiO₂+SnO₂+TiO₂

Substrate sheet+TiO₂+Fe₂O₃

Substrate sheet+Fe₂O₃+TiO₂

Substrate sheet+TiO₂+Al₂O₃+TiO₂

Substrate sheet+TiO₂+ZrO₂+TiO₂。

Effect pigment very particularly preferably has with understructure:

Natural mica thin slice+TiO₂

Natural mica thin slice+titanium oxynitride

Synthetic mica thin slice+TiO₂

Synthetic mica thin slice+titanium oxynitride

Al₂O₃Thin slice+TiO₂

Al₂O₃Thin slice+titanium oxynitride

SiO₂Thin slice+TiO₂

SiO₂Thin slice+titanium oxynitride

Glass thin slice+TiO₂

Glass thin slice+titanium oxynitride

Fe₂O₃Thin slice+TiO₂

Fe₂O₃Thin slice+titanium oxynitride

TiO₂Thin slice+TiO₂

TiO₂Thin slice+ZrO₂+TiO₂

TiO₂Thin slice+SiO₂+TiO₂。

It is certain lower section to be shown in by the commercially available effect pigment that coating for example according to the present invention covers.

* the granularity quoted is the d measured using Malvern 2000 in each case₁₀–d₉₀Value.

In the disclosure in this patent, the refractive index of " high refractive index " expression>=1.8, and " low-refraction " expression refractive index< 1.8。

It is often built to improve wetability, dispersibility and/or compatibility with respective application medium according to application field View makes finished product effect pigment coat or post-process after inorganic and/or is organic, such as uses silane treatment.After suitable coating or Post-processing is to retouch in such as DE patent 22 15 191, DE-A 31 51 354, DE-A 32 35 017 or DE-A 33 34 598 The method stated.The rear coating simplifies pigment processing, especially mixes in various media.

Compared with not stabilized effect pigment, effect pigment according to the present invention has the temperature and thermostabilization of enhancing Property.Stabilized effect pigment can be unquestionably incorporated into engobe and glaze.According to required effect, glaze be can be It is lacklustre, it is also possible to be clear to opaque.

Coating pottery, glassware and ceramic are to improve (filling) surface by fineness or color usually using pottery Porcelain coating composition carries out.Engobe is usually made of frit, adhesive and optional pigment.The engobe generally comprises use In firing 600-1200 DEG C of range of sintering feed, wherein the sintering feed by usually in sintering feed at being grouped as, such as Al₂O₃、SiO₂、B₂O₃、TiO₂、ZrO₂、Sb₂O₃、P₂O₅、Fe₂O₃, alkali metal oxide and alkaline earth oxide.In addition to basis Except effect pigment of the invention, inorganic colored pigments, for example, selected from Co, Cr, Cu, Mn, Fe, Zr, V, Al, Ni, Si, Sb, Pr, Ca or CdSSe (capsule dress) and its nonferrous metal oxides and/or metal hydroxides of mixture can be further with 0-30 Weight %, preferably 5-20 weight %, and especially 5-15 weight % is added in sintering feed, the amount based on inorganic component.

Other than effect pigment, engobe slurry can further include 0-70 weight %, preferably 10-60 weight %, especially It is the adhesive of 20-50 weight %.The selection of adhesive depends on the technical requirements for the coating to be produced.Suitable adhesive is special It is not the usual all adhesives or binder combination considered for ceramics, especially wire mark medium.Therefore, it can be used and be based on Cellulose, polyethylene glycol, nitrocellulose, alkylcellulose, hydroxylated cellulose, hydroxyalkyl cellulose ether, hydroxy alkyl cellulose, Cellulose acetopropionate and butyrate, polyacrylate resin, polymethacrylate resin, polyester resin, polyphenol resin, urine Plain resin, polyterpene resin, polyvinyl resin, Corvic, polyvinyl pyrrolidone resin, gathers melamine resin Styrene and modified polystyrene, poly alpha methylstyrene, hydrogenated wood rosin glycerol ester, polyolefin, coumarone-indene resin, hydrocarbon resin, ketone Resin, urea formaldehyde, anime, formaldehyde resin, carbamic acid resin, sulphamide resin, epoxy resin, polyurethane and/or day So adhesive of oil or the material derivant.In addition, common surface covering adhesive, such as polyurethane-acrylate tree Rouge, acrylate-melamine resin, alkyd resin, polyester resin, polyurethane, nitrocellulose, ketone resin, urea formaldehyde and Polyvinyl butyral, acrylate or epoxy resin and its mixture.

However, the application can also carry out in the case where no adhesive, such as with dust form.In this case, By effect pigment and sintering feed powder dry mixed and apply, such as passes through scattering.

If necessary to solvent, then engobe must be starched in a manner of profession in solvent composition and corresponding adhesive Match.During the preparation process, it can be used water and all organic solvents, it preferably can be with water emulsification or those of miscible.Suitable solvent Be so far used in the ceramic coating composition those, such as pine tar, terpinol, ester alcohol, toluene, naphtha, mineral Oil, aliphatic series or aromatic hydrocarbon, ester, vegetable oil, aliphatic alcohol, such as with those of 2-4 carbon atom, such as ethyl alcohol, butanol, ester Alcohol, tridecanol, isopropanol or ketone, such as acetone or methyl ethyl ketone, ethylene glycol or glycol ethers, such as tripropylene glycol methyl ether, Dihydroxypropane single-ether or glycol, such as ethylene glycol and propylene glycol or polyetherdiol, such as polyethylene glycol and polypropylene glycol, or it is more First alcohol, such as aliphatic triol and tetrol with 2-6 carbon atom, such as trimethylolethane, trimethylolpropane, glycerol, 1,2,4-butanetriol, 1,2,6- hexanetriol and pentaerythrite, and the institute from other class compounds or above-mentioned solvent mixture There are other solvents.It is preferable to use Karsten, Lackrohstofftabellen [Coating Raw Material Tables], The solvent listed in 8th edition in 1987.In particular, using the solvent infinitely miscible with water.

Engobe generally comprises the water and/or organic solvent or solvent mixture of 0-90 weight %, preferably 5-80 weight %, Especially 20-70 weight % is starched based on the engobe.

As additional other components, engobe slurry may comprise up to 15 weight %, preferably one kind of 0.1-5 weight % or A variety of viscosity modifiers.These regulators are equally known in the art, and the example is ethyl cellulose, nitrocellulose, hydroxyl Propyl cellulose, hydroxypropyl methyl cellulose, acrylic resin, poly- (vinyl) butyral resin, carboxymethyl cellulose and ethyl Hydroxyethyl cellulose.

Engobe slurry also may include other altered contents, such as dispersing agent, wetting agent, antisettling agent, flow promortor etc..

Engobe comprising frit, optionally other additives, colorant or coloring pigment is starched into grinding, preferably wet-milling extremely Fineness of grind is 0.1-300 μm, preferably 10-20 μm.Finally, effect pigment is mixed into.

By conventional application method, such as spraying, brush, flow coat or dip-coating, finished product engobe can be starched be applied to ceramic tile, Pottery, glass or ceramic surface.It is preferably applied to firing or unfired ceramic tile, firing or unfired pottery and ceramic system Product.Engobe slurry is preferably applied to unfired product.The engobe of application is then starched into drying, is done preferably at 50-200 DEG C Dry 0.5-5h.Finally, the product of coating is roasted a few hours, preferably 2-48h at 400-1200 DEG C.

Engobe comprising effect pigment according to the present invention provides pottery coating, for example, unfired roof sheet tile and Ceramics, such as glaze and unglazed tile have considerable in terms of color and gloss and a possibility that for novel interesting color Improve optical property.

Effect pigment according to the present invention applies also for preparing flowable pigment preparation and drying agent, especially for printing Brush ink and paint vehicle (preferably automobile coating), by pigment according to the present invention, adhesive and optional one or more additive groups At.

The invention further relates to effect pigments according to the present invention in colorant, paint vehicle, printing ink, plastics, ceramic material, glass Purposes in glass, for plastics and paper laser labelling and be used in cosmetic formulations, especially printing ink.In addition, Pigment according to the present invention applies also for preparing pigment preparation and prepares drying agent, such as particle, thin slice, pellet, agglomerate etc.. Drying agent is especially suitable for paint vehicle and printing ink.

Therefore, the invention further relates to the preparations comprising effect pigment according to the present invention.

Following embodiment is intended to explain the present invention, rather than is limited.

Embodiment 1

By 100g103 (the TiO from Merck₂/ pigments, mica) it is stirred into 2 liters of demineralized waters simultaneously It is heated to 70 DEG C.Then metered 32% antimony chloride of 60g (III) solution passes through during this period while 32% hydroxide is added dropwise Sodium solution keeps pH value constant 4.5.After adding, it is stirred for 30 minutes.Product is filtered out, is washed, dry 10 is small at 110 DEG C When, then calcined 30 minutes at 850 DEG C.Then it is sieved.Obtain that there is white main body tone, high gloss and following granularity point The effect pigment of cloth:

D₁₀=10 μm

D₉₀=60 μm

At a temperature of stabilization of the effect pigment of embodiment 1 at > 1000 DEG C.

Embodiment 2

By 100gCrystal Silver (is coated with TiO₂Al₂O₃Thin slice, the effect from Merck Answer pigment) it is suspended in 2 liters of demineralized waters, and suspension is heated to 85 DEG C.Then metered 32% antimony chloride of 55g (III) solution keeps pH value constant 4.5 by the way that 32% sodium hydroxide solution is added dropwise simultaneously during this period.After adding, it is stirred for 30 Minute.Product is filtered out, is washed, it is 12 hours dry at 110 DEG C, then calcined 45 minutes at 850 DEG C.Then it is sieved. To have white main body tone, very high glaze, very intense flash effect and following size distribution effect pigment:

D₁₀=5 μm

D₉₀=30 μm

At a temperature of stabilization of the effect pigment of embodiment 2 at > 1100 DEG C.

Embodiment 3

By 100gCosmic Silver (coating TiO₂Glass flake, the effect face from Merck Material) it is suspended in 2 liters of demineralized waters, and suspension is heated to 85 DEG C.Then metered 32% antimony chloride of 55g (III) Solution keeps pH value constant 4.5 by the way that 32% sodium hydroxide solution is added dropwise simultaneously during this period.After adding, it is stirred for 30 minutes. Product is filtered out, is washed, it is 12 hours dry at 110 DEG C, then calcined 45 minutes at 850 DEG C.Then it is sieved.Had The effect pigment of white main body tone, very high glaze, very intense flash effect and following size distribution:

D₁₀=20 μm

D₉₀=200 μm

At a temperature of stabilization of the effect pigment of embodiment 3 at > 1000 DEG C.

Embodiment 4

100g splitting is stirred into 2 liters of demineralized waters and is heated to 70 DEG C.Then metered 90g stannic chloride (IV) solution keeps pH value constant 2.3 by the way that 32% sodium hydroxide solution is added dropwise simultaneously during this period.Then metered 200g Titanium chloride (IV) solution keeps pH value constant 1.9 by the way that 32% sodium hydroxide solution is added dropwise simultaneously during this period.Then it is added dropwise 60g32% antimony chloride (III) solution keeps pH value constant 4.5 by the way that 32% sodium hydroxide solution is added dropwise simultaneously during this period.Add After complete, it is stirred for 30 minutes.Product is filtered out, is washed, it is 10 hours dry at 110 DEG C, then calcined 30 minutes at 850 DEG C And be then sieved, obtain the effect pigment with white main body tone, high gloss and following size distribution:

D₁₀=10 μm

D₉₀=60 μm

At a temperature of stabilization of the effect pigment of embodiment 4 at > 1000 DEG C.

Embodiment 5

100g splitting is stirred into 2 liters of demineralized waters and is heated to 70 DEG C.Then metered 90g stannic chloride (IV) solution keeps pH value constant 2.3 by the way that 32% sodium hydroxide solution is added dropwise simultaneously during this period.Then metered 200g Titanium chloride (IV) solution keeps pH value constant 1.9 by the way that 32% sodium hydroxide solution is added dropwise simultaneously during this period.Then it is added dropwise 60g32% antimony chloride (III) solution keeps pH value constant 4.5 by the way that 32% sodium hydroxide solution is added dropwise simultaneously during this period.Add After complete, it is stirred for 30 minutes.Product is filtered out, is washed, it is 10 hours dry at 110 DEG C, 30 points are then calcined at 850 DEG C Clock.Then it is sieved.Obtain the effect pigment with white main body tone, moderate gloss and following size distribution:

D₁₀=5 μm

D₉₀=25 μm

At a temperature of stabilization of the effect pigment of embodiment 5 at > 1000 DEG C.

Embodiment 6

By 100g100 (coating TiO₂Splitting, the effect pigment from Merck) be stirred into 2 liters In demineralized water and it is heated to 70 DEG C.Then metered 60g32% antimony chloride (III) solution, during this period by simultaneously 32% sodium hydroxide solution, which is added dropwise, keeps pH value constant 4.5.After adding, it is stirred for 30 minutes.Product is filtered out, is washed, 110 It is 10 hours dry at DEG C, then calcined 30 minutes at 1000 DEG C.Then it is sieved.Obtain that there is white main body tone, high glaze The effect pigment of degree and following size distribution:

D₁₀=10 μm

D₉₀=60 μm

At a temperature of stabilization of the effect pigment of embodiment 6 at > 1000 DEG C.

Embodiment 7

By 100g123 (coating TiO₂Splitting, the effect pigment from Merck) be stirred into 2 liters In demineralized water and it is heated to 70 DEG C.Then metered 60g32% stannic chloride (IV)/antimony (III) solution, leads to during this period It crosses while 32% sodium hydroxide solution, which is added dropwise, keeps pH value constant 4.5.After adding, it is stirred for 30 minutes.Product is filtered out, is washed It washs, it is 10 hours dry at 110 DEG C, then calcined 30 minutes at 850 DEG C.Then it is sieved.Obtain having white main body tone, The effect pigment of moderate gloss and flash effect and following size distribution:

D₁₀=5 μm

D₉₀=25 μm

At a temperature of stabilization of the effect pigment of embodiment 7 at > 1000 DEG C.

Embodiment 8

By 100g6163 (coating TiO₂Synthetic mica thin slice, the effect pigment from Merck) suspend 85 DEG C are heated in 2 liters of demineralized waters, and by suspension.Then metered 32% antimony chloride of 55g (III) solution, In Keep pH value constant 4.5 by the way that 32% sodium hydroxide solution is added dropwise simultaneously during this.After adding, it is stirred for 30 minutes.By product It filters out, washs, it is 12 hours dry at 110 DEG C, then calcined 45 minutes at 850 DEG C.Then it is sieved.Obtain having white main The effect pigment of body colour tune, high gloss and intense flash effect and following size distribution:

D₁₀=20 μm

D₉₀=180 μm

At a temperature of stabilization of the effect pigment of embodiment 8 at > 1000 DEG C.

Embodiment 9

By 100gViola Fantasy (coating TiO₂SiO₂Thin slice, the effect from Merck Answer pigment) it is suspended in 2 liters of demineralized waters, and suspension is heated to 85 DEG C.Then metered 32% antimony chloride of 55g (III) solution keeps pH value constant 4.5 by the way that 32% sodium hydroxide solution is added dropwise simultaneously during this period.After adding, it is stirred for 30 Minute.Product is filtered out, is washed, it is 12 hours dry at 110 DEG C, then calcined 45 minutes at 850 DEG C.Then it is sieved. To the effect pigment with white main body tone, very high gloss, changeable colors along with angle and following size distribution:

D₁₀=5 μm

D₉₀=50 μm

At a temperature of stabilization of the effect pigment of embodiment 9 at > 1000 DEG C.

Embodiment 10

By 100g183 (coating TiO₂Splitting, the effect pigment from Merck) be stirred into 2 liters In demineralized water and it is heated to 70 DEG C.Then metered 60g32% antimony chloride (III) solution, during this period by simultaneously 32% sodium hydroxide solution, which is added dropwise, keeps pH value constant 4.5.After adding, it is stirred for 30 minutes.Product is filtered out, is washed, 110 It is 10 hours dry at DEG C, then calcined 30 minutes at 1000 DEG C.Then it is sieved.Obtain that there is white main body tone, high glaze The effect pigment of degree, intense flash effect and following size distribution:

D₁₀=45 μm

D₉₀=500 μm

At a temperature of stabilization of the effect pigment of embodiment 10 at > 1000 DEG C.

The improvement stability of the pigment prepared in embodiment 1-10 is in each case by compared with non-stable pigments Application specific is tested to prove.For this purpose, in an identical manner using unstabilized pigment (such as in embodiment 1103) stable pigment and in each case, and visually evaluate the color and pearly-lustre of two kinds of workpiece Effect.Compared with corresponding commercially available or non-stabilizing effect pigment, stabilized pigment displays go out less discoloration in each case With better pearl effect.

As representative, the silk-screen printing for porcelain workpiece can be mentioned that herein, be divided into 3 steps.

1) printing slurry is prepared:

In order to prepare fine color grid and relief-type printed matter on ceramic base material by ceramic color, screen printing is used Brush oil prevents the printed matter of flowing and generation with clear profile of mill base after printing.For this purpose, adding using known binders Add agent, is made of natural or synthetic wax fine crushing and/or inorganic silicate fine crushing or oxidation material, the inorganic silicate Or oxidation material can mix in the silicate sturcture of fluxing agent in sintering procedure.By with corresponding amount sintering feed and printing Medium (silk-screen printing oil 221-ME and Screenprint Bulk 803035MR- both commercial product-use from Ferro In embodiment) pearlescent pigment weigh and be homogenized to carry out a series of experiment:

Weigh up the sintering feed homogenizing of the effect pigment according to embodiment 1-10 and the consisting of with corresponding amount:

Sintering feed	CaO	Na₂O	K₂O	BaO	Al₂O₃	SiO₂	B₂O₃
								Wt%	9.7	5.2	1.1	1.3	10.1	69.6	3.0

Following steps are unrelated with the composition of printing slurry.

2) ceramic tile is printed

The printing slurry of acquisition can be applied on ceramic tile by standard printing process, sliding method, spray coating method or trans-printing. In all cases, the at a temperature of drying by the ceramic tile through printing in drying box or draught cupboard at 60-110 DEG C, to evaporate print Solvent present in brush oil.In an embodiment according to the present invention, printing slurry is applied to by porcelain by scraper and silk-screen printing On brick.

3) printing ceramic tile is fired

Then the ceramic tile for being printed and being dried is fired in combustion furnace by temperature curve.

180min: being heated to 1100 DEG C,

3min: being held in 1100 DEG C,

120min: being quickly cooled to 600 DEG C,

300min: it is slowly cooled to room temperature.

Claims

1. being characterized in that the pigment has on its surface by one or more sb oxides based on the effect pigment of laminar substrate Or the coating that sb oxide mixture is constituted.

2. effect pigment according to claim 1 is characterized in that the effect pigment has on its surface by Sb_xO_yThe covering of composition Layer, wherein x=2 and y=3,4,5.

3. effect pigment according to claim 1 or 2 is characterized in that the coating by Sb₂O₄Composition.

4. -3 one or more effect pigment according to claim 1 is characterized in that the amount of the coating accounts for 5-50 weight %, base In total pigment meter.

5. -4 one or more effect pigment according to claim 1 is characterized in that the coating has the thickness of 1-100nm.

6. -5 one or more effect pigment according to claim 1 is characterized in that the effect pigment is selected from pearlescent pigment, interference Pigment, multi-layer pigments and holographic pigment.

7. -6 one or more effect pigment according to claim 1 is characterized in that the effect pigment based on natural or synthetic Splitting, SiO₂Thin slice, glass flake, TiO₂Thin slice or Al₂O₃Thin slice.

8. -7 one or more effect pigment according to claim 1 is characterized in that the effect pigment wraps on laminar substrate Containing at least one TiO₂Layer and/or at least one oxynitriding titanium layer.

9. -8 one or more effect pigment according to claim 1 is characterized in that the effect pigment has a structure that

Substrate sheet+TiO₂

Substrate sheet+titanium oxynitride

Substrate sheet+SiO₂+TiO₂

Substrate sheet+SnO₂+TiO₂

Substrate sheet+Cr₂O₃+TiO₂

Substrate sheet+Ce₂O₃+TiO₂

Substrate sheet+ZrO₂+TiO₂

Substrate sheet+TiO₂+Cr₂O₃

Substrate sheet+TiO₂+SiO₂+TiO₂

Substrate sheet+TiO₂+SiO₂

Substrate sheet+TiO₂+SnO₂+TiO₂

Substrate sheet+TiO₂+Fe₂O₃

Substrate sheet+Fe₂O₃+TiO₂

Substrate sheet+TiO₂+Al₂O₃+TiO₂

Substrate sheet+TiO₂+ZrO₂+TiO₂。

10. -9 one or more effect pigment according to claim 1 is characterized in that the effect pigment is selected from following effect face Material:

Natural mica thin slice+TiO₂

Natural mica thin slice+titanium oxynitride

Synthetic mica thin slice+TiO₂

Synthetic mica thin slice+titanium oxynitride

Al₂O₃Thin slice+TiO₂

Al₂O₃Thin slice+titanium oxynitride

SiO₂Thin slice+TiO₂

SiO₂Thin slice+titanium oxynitride

Glass flake+TiO₂

Glass flake+titanium oxynitride

Fe₂O₃Thin slice+TiO₂

Fe₂O₃Thin slice+titanium oxynitride

TiO₂Thin slice+TiO₂

TiO₂Thin slice+ZrO₂+TiO₂

TiO₂Thin slice+SiO₂+TiO₂。

11. the method for preparing -10 one or more effect pigments according to claim 1, is characterized in that passing through wet chemical method Or sb oxide layer is applied to by effect pigment by gas phase cladding process.

12. -10 one or more effect pigments are in colorant, paint vehicle, printing ink, plastics, ceramic material according to claim 1 Material, the purposes in glass are used in cosmetic formulations for the laser labelling of plastics and paper, be used to prepare pigment preparation and Drying agent.

13. the purposes of effect pigment according to claim 12, the coloring for glaze, engobe and enamel.

14. the preparation comprising -10 one or more effect pigments according to claim 1.